Supramolecular complexes [M{NH(CH2)4O}{S2CN(C2H5)2 2] ∙ CCl4 (M = Zn or 63Cu(II)): Synthesis, structures, spectral and thermal properties

Abstract

Solvated adducts of diethyldithiocarbamate complexes of zinc and copper(II) of the formula [M{NH(CH2)4O}{S2CN(C2H5)22] ∙ CCl4 (M = Zn (I) and 63Cu (II)) were obtained. 13C MAS NMR experiments revealed magnetic nonequivalence in the dithiocarbamate moieties of the adduct isomers, the morpholine heterocycles, and the outer-sphere solvate molecules. The rhombic anisotropy of the EPR parameters of magnetically diluted isotope-substituted complex II is due to the copper polyhedron geometry, which is intermediate between a tetragonal pyramid and a trigonal bipyramid, with the ground state of the unpaired electron resulting from the mixing \(3{d_{{x^2} - {y^{2 - }}}}\) of and \(3{d_{{z^{2 - }}}}\) of copper(II). According to X-ray diffraction data, complex I is a supramolecular complex combining structurally nonequivalent adduct molecules (A and B) and “guest” molecules (CCl4). In addition, the crystal lattice has an array of channels occupied by outersphere solvate CCl4 molecules (a structural type of lattice clathrates). An STA study of the thermal properties revealed three main thermolysis steps: desorption of the solvate CCl4 molecules, elimination of coordinated morpholine molecules, and thermolysis of the dithiocarbamate moiety of the adduct.